JP7176469B2 - Siloxane polymer containing isocyanuric acid skeleton and polyether skeleton, photosensitive resin composition, pattern forming method, and method for producing optical semiconductor element - Google Patents

Description

TECHNICAL FIELD The present invention relates to a siloxane polymer containing an isocyanuric acid skeleton and a polyether skeleton, a photosensitive resin composition, a pattern forming method, and a method for producing an optical semiconductor element.

Epoxy resin has been mainly used as a sealing protective material for various optical devices represented by light-emitting diodes (LEDs), CMOS image sensors, and the like. Among them, many epoxy-modified silicone resins have been used as those having high transparency and light resistance, and there is also a type in which an alicyclic epoxy group is introduced into the silphenylene skeleton (Patent Document 1).

Even if there is no problem with light resistance for conventional devices, optical devices such as LEDs are becoming more and more powerful in recent years. There were problems such as discoloration. In recent years, many optical devices also require microfabrication. Various resist materials, typified by epoxy resin materials, have been used for such microfabrication. However, the epoxy-modified silicone resin described above is not a material that can be finely processed to a size of about 10 μm. As an epoxy resin applicable to resist materials, there is a type in which silphenylene modified with alicyclic epoxy at both ends is introduced as a cross-linking agent (Patent Document 2). However, it cannot be said that the light resistance is sufficient, and there has been a demand for a material that can provide a film that can withstand even more severe conditions.

Japanese Patent Publication No. 8-32763 JP 2012-001668 A

The present invention has been made in view of the above circumstances, and provides a novel polymer that can provide a film with high transparency and high light resistance, and a polymer that enables fine pattern formation in a wide range of wavelengths, while maintaining high transparency and high light resistance after pattern formation. An object of the present invention is to provide a photosensitive resin composition capable of providing a light-resistant and highly heat-resistant film, a pattern forming method using the photosensitive resin composition, and a method for manufacturing an optical semiconductor element.

The inventors of the present invention have made intensive studies to achieve the above object, and found that a polymer containing a polysiloxane skeleton, a silphenylene skeleton, an isocyanuric acid skeleton and a polyether skeleton in the main chain and an epoxy group in the side chain is high. By providing a transparent and highly light-resistant film, and by the photosensitive resin composition containing the polymer and the photoacid generator, it is possible to form a fine pattern in a wide range of wavelengths, while maintaining high transparency and high light resistance after pattern formation. The present inventors have completed the present invention based on the discovery that a film having high light resistance and high heat resistance can be obtained.

［式中、Ｒ¹～Ｒ⁴は、それぞれ独立に、ヘテロ原子を含んでいてもよい炭素数１～２０の１価炭化水素基である。ｍは、それぞれ独立に、１～６００の整数である。ｍが２以上の整数のとき、各Ｒ³は、互いに同一であっても異なっていてもよく、各Ｒ⁴は、互いに同一であっても異なっていてもよい。ａ¹、ａ²、ａ³及びａ⁴は、０＜ａ¹＜１、０＜ａ²＜１、０＜ａ³＜１、０＜ａ⁴＜１、及びａ¹＋ａ²＋ａ³＋ａ⁴＝１を満たす数である。Ｘ¹は、下記式（Ｘ１）で表される２価の基である。Ｘ²は、下記式（Ｘ２）で表される２価の基である。

（式中、Ｒ¹¹及びＲ¹²は、それぞれ独立に、水素原子又はメチル基である。ｎ¹及びｎ²は、それぞれ独立に、０～７の整数である。Ｒ¹³は、炭素数１～８の２価炭化水素基であり、その炭素原子間にエステル結合又はエーテル結合を含んでいてもよい。）

（式中、Ｒ²¹及びＲ²²は、それぞれ独立に、水素原子、又は炭素数１～８の１価炭化水素基である。Ｒ²³及びＲ²⁴は、それぞれ独立に、水素原子又はメチル基である。ｐ¹及びｐ²は、それぞれ独立に、１～６の整数である。ｑは、０～１００の整数である。）］
４．ｑが、５～２０の整数である３のシロキサンポリマー。
５．ｍが、１０～１００の整数である３又は４のシロキサンポリマー。
６．Ｒ¹¹、Ｒ¹²、Ｒ²¹及びＲ²²が、水素原子である３～５のいずれかのシロキサンポリマー。
７．重量平均分子量が３,０００～５００,０００である１～６のいずれかのシロキサンポリマー。
８．（Ａ）１～７のいずれかのシロキサンポリマー及び（Ｂ）光酸発生剤を含む感光性樹脂組成物。
９．（Ｂ）成分の含有量が、（Ａ）成分１００質量部に対し、０.０５～２０質量部である８の感光性樹脂組成物。
１０．更に、（Ｃ）カチオン重合性架橋剤を含む８又は９の感光性樹脂組成物。
１１．更に、（Ｄ）溶剤を含む８～１０のいずれかの感光性樹脂組成物。
１２．更に、（Ｅ）酸化防止剤を含む８～１１のいずれかの感光性樹脂組成物。
１３．（ｉ）８～１２のいずれかの感光性樹脂組成物を用いて基板上に感光性樹脂皮膜を形成する工程、
（ii）前記感光性樹脂皮膜を露光する工程、及び
（iii）前記露光した感光性樹脂皮膜を、現像液を用いて現像する工程
を含むパターン形成方法。
１４．１３のパターン形成方法を含む、感光性樹脂皮膜を備える光半導体素子の製造方法。 Accordingly, the present invention provides the following siloxane polymer, photosensitive resin composition, pattern forming method, and optical semiconductor device manufacturing method.
1. A siloxane polymer containing a polysiloxane skeleton, a silphenylene skeleton, an isocyanuric acid skeleton and a polyether skeleton in the main chain and an epoxy group in the side chain.
2. 1. The siloxane polymer according to 1, wherein the transmittance of light having a wavelength of 405 nm is 97% or more in a 10 μm-thick film made of the above polymer.
3. 1 or 2 siloxane polymers containing repeating units represented by the following formulas (A1) to (A4).

[In the formula, R ¹ to R ⁴ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. Each m is independently an integer from 1 to 600. When m is an integer of 2 or more, each R ³ may be the same or different, and each R ⁴ may be the same or different. a1 ^{, a2} , a3 and a4 are ⁰ <a1< ^{1 ,} 0<a2< ¹ , 0<a3< ¹ , ⁰ <a4< ¹ and a1+ ^a2 + ^a3 + ^a4 = 1 is a number that satisfies. X ¹ is a divalent group represented by the following formula (X1). X ² is a divalent group represented by the following formula (X2).

(wherein R ¹¹ and R ¹² are each independently a hydrogen atom or a methyl group; n ¹ and n ² are each independently an integer of 0 to 7; R ¹³ has 1 to 8 divalent hydrocarbon group, which may contain an ester bond or an ether bond between its carbon atoms.)

(wherein R ²¹ and R ²² are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms; R ²³ and R ²⁴ are each independently a hydrogen atom or a methyl group; p ¹ and p ² are each independently an integer of 1 to 6. q is an integer of 0 to 100.)]
4. A siloxane polymer of 3 wherein q is an integer from 5-20.
5. 3 or 4 siloxane polymers where m is an integer from 10-100.
6. A siloxane polymer according to any one of 3 to 5, wherein R ¹¹ , R ¹² , R ²¹ and R ²² are hydrogen atoms.
7. A siloxane polymer of any one of 1 to 6 having a weight average molecular weight of 3,000 to 500,000.
8. (A) A photosensitive resin composition containing the siloxane polymer according to any one of 1 to 7 and (B) a photoacid generator.
9. The photosensitive resin composition of 8, wherein the content of component (B) is 0.05 to 20 parts by mass per 100 parts by mass of component (A).
10. Furthermore, the photosensitive resin composition of 8 or 9 containing (C) a cationically polymerizable cross-linking agent.
11. Further, (D) the photosensitive resin composition of any one of 8 to 10 containing a solvent.
12. 12. The photosensitive resin composition according to any one of 8 to 11, further comprising (E) an antioxidant.
13. (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition according to any one of 8 to 12;
(ii) a step of exposing the photosensitive resin film; and (iii) a step of developing the exposed photosensitive resin film using a developer.
14. A method of manufacturing an optical semiconductor element having a photosensitive resin film, including the pattern forming method of 13.

The siloxane polymers of the present invention can be easily synthesized and can provide films with high transparency and high lightfastness. In addition, by using the photosensitive resin composition containing the polymer and the photoacid generator, it is possible to easily form a film without being damaged by oxygen, and the film can be exposed to light of a wide range of wavelengths. pattern can be formed. Furthermore, the film obtained from the photosensitive resin composition of the present invention is excellent in transparency, light resistance and heat resistance, and can be suitably used for protecting and encapsulating optical semiconductor elements and the like.

[Siloxane polymer]
The siloxane polymer of the present invention contains a polysiloxane skeleton, a silphenylene skeleton, an isocyanuric acid skeleton and a polyether skeleton in the main chain, and an epoxy group in the side chain.

Such polymers preferably include repeating units represented by the following formulas (A1) to (A4) (hereinafter also referred to as repeating units A1 to A4, respectively).

In formulas (A2) and (A4), R ¹ to R ⁴ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. Each m is independently an integer from 1 to 600. When m is an integer of 2 or more, each R ³ may be the same or different, and each R ⁴ may be the same or different. When there are two or more siloxane units in the repeating units A2 and A4, each siloxane unit may be the same or may contain two or more different siloxane units. When two or more different siloxane units are included (that is, when m is an integer of 2 or more), the siloxane units may be randomly bonded or alternately bonded, and include multiple blocks of the same type of siloxane unit. may be

The monovalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include monovalent aliphatic groups such as alkyl groups having 1 to 20 carbon atoms and alkenyl groups having 2 to 20 carbon atoms. Examples include monovalent aromatic hydrocarbon groups such as hydrocarbon groups, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, norbornyl group, adamantyl group and the like. Examples of the alkenyl group include vinyl group, propenyl group, butenyl group and pentenyl group.

Further, the monovalent aliphatic hydrocarbon group may contain a hetero atom, specifically, some or all of the hydrogen atoms in the monovalent aliphatic hydrocarbon group are fluorine atoms, chlorine atoms , a bromine atom, an iodine atom, or the like, and a carbonyl group, an ether bond, a thioether bond, or the like may be interposed between the carbon atoms. A 2-oxocyclohexyl group etc. are mentioned as such a monovalent|monohydric aliphatic hydrocarbon group containing a hetero atom.

Examples of the aryl group include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group, and 4-tert-butyl. phenyl group, 4-butylphenyl group, dimethylphenyl group, naphthyl group, biphenylyl group, terphenylyl group and the like. A benzyl group, a phenethyl group, etc. are mentioned as said aralkyl group.

In addition, the monovalent aromatic hydrocarbon group may contain a hetero atom. Specifically, some or all of the hydrogen atoms in the monovalent aromatic hydrocarbon group have 1 to 10 carbon atoms. alkoxy group, alkylthio group having 1 to 10 carbon atoms, aryloxy group having 6 to 20 carbon atoms, arylthio group having 6 to 20 carbon atoms, or the like.

Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, cyclopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group and tert-butyloxy group. group, cyclobutyloxy group, n-pentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, nor A bornyloxy group, an adamantyloxy group, and the like can be mentioned.

Examples of the alkylthio group having 1 to 10 carbon atoms include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, cyclopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group and tert-butylthio group. , cyclobutylthio group, n-pentylthio group, cyclopentylthio group, n-hexylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group, n-nonylthio group, n-decylthio group, norbornylthio group, adamantylthio group and the like.

Examples of the aryloxy group having 6 to 20 carbon atoms include a phenyloxy group, a 2-methylphenyloxy group, a 3-methylphenyloxy group, a 4-methylphenyloxy group, a 2-ethylphenyloxy group and a 3-ethylphenyloxy group. group, 4-ethylphenyloxy group, 4-tert-butylphenyloxy group, 4-butylphenyloxy group, dimethylphenyloxy group, naphthyloxy group, biphenylyloxy group, terphenylyloxy group and the like.

Examples of the arylthio group having 6 to 20 carbon atoms include a phenylthio group, a 2-methylphenylthio group, a 3-methylphenylthio group, a 4-methylphenylthio group, a 2-ethylphenylthio group, a 3-ethylphenylthio group, 4-ethylphenylthio group, 4-tert-butylphenylthio group, 4-butylphenylthio group, dimethylphenylthio group, naphthylthio group, biphenylylthio group, terphenylylthio group and the like.

For example, aryl groups substituted with these groups include 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 3-tert-butoxyphenyl group, 4-tert-butoxyphenyl group, biphenylyloxyphenyl group, biphenylylthiophenyl group and the like.

The number of carbon atoms in the monovalent aliphatic hydrocarbon group is preferably 1-10, more preferably 1-8. The number of carbon atoms in the monovalent aromatic hydrocarbon group is preferably 1-14, more preferably 1-10.

Among these, R ¹ to R ⁴ are preferably methyl group, ethyl group, n-propyl group or phenyl group, more preferably methyl group or phenyl group.

In formulas (A2) and (A4), m is each independently an integer of 1-600, preferably an integer of 8-100.

In formulas (A1) to (A4), a ¹ , a ² , a ³ and a ⁴ are 0<a ¹ <1, 0<a ² <1, 0<a ³ <1, 0<a ⁴ <1 , and a ¹ +a ² +a ³ +a ⁴ =1. Preferably, ^0.010≤a1 +a2≤0.490, ^{0.010≤a3 + a4≤0.490 , 0.050≤a1 + a3≤0.490} , 0.010≤a2+a4 ≤ 0.450 and a ¹ + a ² + a ³ + a ⁴ = 1, more preferably 0.050 ≤ a ¹ + a ² ≤ 0.450 and 0.050 ≤ a ³ + a ⁴ ≤ 0.050. 450, 0.200≦a ¹ +a ³ ≦0.450, 0.050≦a ² +a ⁴ ≦0.300, and a ¹ +a ² +a ³ +a ⁴ =1.

In formulas (A1) and (A2), X ¹ is a divalent group represented by formula (X1) below.

In formula (X1), R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group. n ¹ and n ² are each independently an integer of 0-7.

In formula (X1), R ¹³ is a divalent hydrocarbon group having 1 to 8 carbon atoms and may contain an ester bond or an ether bond between the carbon atoms. The divalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane- Alkanediyl groups such as 1,2-diyl group, propane-1,3-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, and the like. be done. Moreover, an ester bond or an ether bond may be interposed between the carbon atoms of the divalent hydrocarbon group. Among these, R ¹³ is preferably a methylene group or an ethylene group, more preferably a methylene group.

In formulas (A3) and (A4), X ² is a divalent group represented by formula (X2) below.

In formula (X2), R ²¹ and R ²² are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. ^R23 and ^R24 are each independently a hydrogen atom or a methyl group. Each of p ¹ and p ² is independently an integer of 1 to 6, preferably an integer of 1 to 4, more preferably 1 or 2. q is an integer of 0-100, preferably an integer of 1-50, more preferably an integer of 5-20.

The monovalent hydrocarbon group having 1 to 8 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include alkyl groups having 1 to 8 carbon atoms and alkenyl groups having 2 to 8 carbon atoms. and monovalent aromatic hydrocarbon groups such as aryl groups having 6 to 8 carbon atoms and aralkyl groups having 7 or 8 carbon atoms.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and cyclobutyl group. , n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and the like. Examples of the alkenyl group include vinyl group, propenyl group, butenyl group and pentenyl group.

Examples of the aryl group include a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, dimethylphenyl group and the like. mentioned. A benzyl group, a phenethyl group, etc. are mentioned as said aralkyl group.

R ²¹ and R ²² are preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or a methyl group.

In formula (X2), the alkylene oxide units represented by the subscript q may be randomly bonded or alternately bonded, and may contain a plurality of blocks of the same type of alkylene oxide units.

The siloxane polymer of the present invention preferably has a weight average molecular weight (Mw) of 3,000 to 500,000, more preferably 5,000 to 200,000. If the Mw is within the above range, the polymer can be obtained as a solid, and the film formability can be ensured. In the present invention, Mw is a value measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an elution solvent.

The siloxane polymer of the present invention may be one in which the repeating units A1 to A4 are randomly or alternately linked, and may contain multiple blocks of each unit. Moreover, in the siloxane polymer of the present invention, the content of siloxane units is preferably 10 to 90% by mass.

[Method for producing siloxane polymer]
The siloxane polymer of the present invention includes a compound represented by the following formula (1) (hereinafter also referred to as compound (1)) and a compound represented by the following formula (2) (hereinafter also referred to as compound (2). ), a compound represented by the following formula (3) (hereinafter also referred to as compound (3)), and a compound represented by the following formula (4) (hereinafter also referred to as compound (4)), It can be produced by addition polymerization in the presence of a metal catalyst.

（式中、Ｒ¹～Ｒ⁴、Ｒ¹¹～Ｒ¹³、Ｒ²¹～Ｒ²⁴、ｍ、ｎ¹、ｎ²、ｐ¹、ｐ²及びｑは、前記と同じ。）

(Wherein, R ¹ to R ⁴ , R ¹¹ to R ¹³ , R ²¹ to R ²⁴ , m, n ¹ , n ² , p ¹ , p ² and q are the same as above.)

Examples of the metal catalyst include simple platinum group _metals such as _{platinum (} including _{platinum black} ), _rhodium , and _{palladium ; 6.xH2O} , _{Na2PtCl6.xH2O , K2PtCl4.xH2O , PtCl4.xH2O , PtCl2 , Na2HPtCl4.xH2O ( where x} is ₀ platinum chloride, chloroplatinic acid and chloroplatinic acid salts such as platinum chloride, chloroplatinic acid and chloroplatinic acid salts (for example, those described in US Pat. No. 3,220,972); Complexes of chloroplatinic acid with olefins (e.g., those described in U.S. Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); platinum group metals such as platinum black and palladium supported on a carrier such as alumina, silica, carbon; rhodium - olefin complex; chlorotris (triphenylphosphine) rhodium (so-called Wilkinson catalyst); platinum chloride, chloroplatinic acid or chloroplatinate and vinyl group-containing siloxane ( In particular, a complex with a vinyl group-containing cyclic siloxane) or the like can be used.

The amount of the catalyst used is a catalytic amount, and is usually preferably 0.001 to 0.1% by mass as platinum group metal in the total mass of compounds (1) to (4).

If necessary, a solvent may be used in the polymerization reaction. As the solvent, for example, hydrocarbon solvents such as toluene and xylene are preferable. As for the polymerization conditions, the polymerization temperature is preferably 40 to 150° C., particularly 60 to 120° C., from the viewpoint that the catalyst is not deactivated and the polymerization can be completed in a short time. Although the polymerization time depends on the kind and amount of the raw material compounds, it is preferable to complete the polymerization in about 0.5 to 100 hours, particularly 0.5 to 30 hours, in order to prevent moisture from entering the polymerization system. After completion of the polymerization reaction in this manner, the polymer can be obtained by distilling off the solvent if used.

The reaction method is not particularly limited, but first, compound (3) and compound (4) are mixed and heated, then a metal catalyst is added to the mixed solution, and then compound (1) and compound (2) are added to 0. It is recommended to drip over 1 to 5 hours.

In each raw material compound, the molar ratio of the hydrosilyl groups of compound (1) and compound (2) to the total alkenyl groups of compound (3) and compound (4) is preferably 0.67 to 1. 67, more preferably 0.83 to 1.25. The Mw of the siloxane polymers of the present invention can be controlled by using monoallyl compounds such as o-allylphenol or monohydrosilanes such as triethylhydrosilane or monohydrosiloxanes as molecular weight modifiers.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention contains (A) the siloxane polymer described above and (B) a photoacid generator. The (A) component siloxane polymer may be used singly or in combination of two or more.

[(B) Photoacid generator]
The photoacid generator of component (B) is not particularly limited as long as it is decomposed by light irradiation to generate an acid. (B) The photoacid generator is used as a curing catalyst. Examples of the photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzylsulfonate derivatives, sulfonic acid ester derivatives, imido-yl-sulfonate derivatives, oximesulfonate derivatives, iminosulfonate. derivatives, triazine derivatives and the like.

Examples of the onium salts include sulfonium salts represented by the following formula (B1) and iodonium salts represented by the following formula (B2).

In formulas (B1) and (B2), R ¹⁰¹ to R ¹⁰⁵ are each independently an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted carbon number It is an aryl group of 6 to 12 or an aralkyl group of 7 to 12 carbon atoms which may have a substituent. A ⁻ is the non-nucleophilic counterion.

The alkyl group may be linear, branched or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl and sec-butyl. group, tert-butyl group, cyclobutyl group, n-pentyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group and the like. A phenyl group, a naphthyl group, a biphenylyl group, etc. are mentioned as said aryl group. A benzyl group, a phenethyl group, etc. are mentioned as said aralkyl group.

Examples of the substituents include an oxo group, a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and 6 to 24 carbon atoms. aryl group, aralkyl group having 7 to 25 carbon atoms, aryloxy group having 6 to 24 carbon atoms, arylthio group having 6 to 24 carbon atoms, and the like.

R ¹⁰¹ to R ¹⁰⁵ are optionally substituted alkyl groups such as methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, norbornyl group, adamantyl group and 2-oxocyclohexyl group; phenyl group; , naphthyl group, biphenylyl group, o-, m- or p-methoxyphenyl group, ethoxyphenyl group, m- or p-tert-butoxyphenyl group, 2-, 3- or 4-methylphenyl group, ethylphenyl group, Aryl groups optionally having substituents such as 4-tert-butylphenyl group, 4-butylphenyl group, dimethylphenyl group, terphenylyl group, biphenylyloxyphenyl group, biphenylylthiophenyl group; benzyl group, phenethyl An aralkyl group optionally having a substituent such as a group is preferred. Among these, an optionally substituted aryl group and an optionally substituted aralkyl group are more preferable.

Examples of the non-nucleophilic counter ions include halide ions such as chloride ion and bromide ion; arylsulfonate ions such as rate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion, 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkanesulfonate ion such as mesylate ion and butanesulfonate ion; trifluoromethane fluoroalkanesulfonimide ions such as sulfonimide ions; fluoroalkanesulfonylmethide ions such as tris(trifluoromethanesulfonyl)methide ions; borate ions such as tetrakisphenylborate ions and tetrakis(pentafluorophenyl)borate ions;

Examples of the diazomethane derivative include compounds represented by the following formula (B3).

In formula (B3), R ¹¹¹ and R ¹¹² are each independently an alkyl group having 1 to 12 carbon atoms or a halogenated alkyl group, an aryl group having 6 to 12 carbon atoms which may have a substituent, or It is an aralkyl group having 7 to 12 carbon atoms.

Examples of the alkyl group include those exemplified in the description of R ¹⁰¹ to R ¹⁰⁵ . Examples of the halogenated alkyl group include trifluoromethyl group, 1,1,1-trifluoroethyl group, 1,1,1-trichloroethyl group and nonafluorobutyl group.

The aryl group optionally having substituents includes a phenyl group; 2-, 3- or 4-methoxyphenyl group, 2-, 3- or 4-ethoxyphenyl group, 3- or 4-tert-butoxy alkoxyphenyl group such as phenyl group; 2-, 3- or 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, alkylphenyl group such as dimethylphenyl group; fluorophenyl group , a chlorophenyl group, a 1,2,3,4,5-pentafluorophenyl group, and other halogenated aryl groups. A benzyl group, a phenethyl group, etc. are mentioned as said aralkyl group.

Examples of the glyoxime derivative include compounds represented by the following formula (B4).

In formula (B4), R ¹²¹ to R ¹²⁴ are each independently an alkyl group having 1 to 12 carbon atoms or a halogenated alkyl group, an aryl group having 6 to 12 carbon atoms which may have a substituent, or It is an aralkyl group having 7 to 12 carbon atoms. In addition, R ¹²³ and R ¹²⁴ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded, and when forming a ring, the group formed by bonding R ¹²³ and R ¹²⁴ is It is a linear or branched alkylene group having 1 to 12 carbon atoms.

Examples of the alkyl group, halogenated alkyl group, optionally substituted aryl group, and aralkyl group include those exemplified for R ¹¹¹ and R ¹¹² . Examples of the linear or branched alkylene group include methylene group, ethylene group, propylene group, butylene group and hexylene group.

Specific examples of the onium salts include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, p-toluenesulfonate (p-tert-butoxy Phenyl)phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate, tris( p-tert-butoxyphenyl)sulfonium, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate , tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, trifluoromethane Cyclohexylmethyl(2-oxocyclohexyl)sulfonium sulfonate, Cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, Dimethylphenylsulfonium trifluoromethanesulfonate, Dimethylphenylsulfonium p-toluenesulfonate, Dicyclohexylphenyl trifluoromethanesulfonate Sulfonium, dicyclohexylphenylsulfonium p-toluenesulfonate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylylthio)phenyl ]-4-biphenylylphenylsulfonium tris(trifluoromethanesulfonyl)methide, triphenylsulfonium tetrakis(fluorophenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]tetrakis(fluorophenyl)borate, tetrakis( Pentafluorophenyl)borate triphenylsulfonate and tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate.

Specific examples of the diazomethane derivatives include bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n- Butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(n- pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert-pentylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1- cyclohexylsulfonyl-1-(tert-pentylsulfonyl)diazomethane, 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane and the like.

Specific examples of the glyoxime derivative include bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-o-(p- toluenesulfonyl)-α-dicyclohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedione glyoxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentane Dionglyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α -dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedioneglyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedioneglyoxime , bis-o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α -dimethylglyoxime, bis-o-(tert-butanesulfonyl)-α-dimethylglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α- Dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl) -α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, bis-o-(camphorsulfonyl)-α-dimethylglyoxime and the like.

Specific examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane.

Specific examples of the disulfone derivative include diphenyldisulfone and dicyclohexyldisulfone.

Specific examples of the nitrobenzylsulfonate derivatives include 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

Specific examples of the sulfonic acid ester derivatives include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, 1,2,3-tris(p- toluenesulfonyloxy)benzene and the like.

Specific examples of the imido-yl-sulfonate derivatives include phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene-2,3 -dicarboximido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-n-butylsulfonate, n-trifluoromethylsulfonyloxynaphthylimide and the like.

Specific examples of the oximesulfonate derivatives include α-(benzenesulfoniumoxyimino)-4-methylphenylacetonitrile.

Specific examples of the iminosulfonate derivatives include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-(4-(4-methyl phenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile;

In addition, 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane and the like can also be preferably used.

As the photo-acid generator of the component (B), the above onium salts are particularly preferred, and the above sulfonium salts are more preferred.

The content of component (B) is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of component (A). If the content of the component (B) is within the above range, it is easy to obtain sufficient photocurability, and it is possible to effectively prevent deterioration of the curability of a thick film due to light absorption by the photoacid generator itself. be able to. In order to obtain the transparency and light resistance which are characteristics of the present invention, the amount of the light-absorbing photoacid generator (B) should be small within a range that does not impede the photocurability. The (B) component photoacid generator may be used alone or in combination of two or more.

[(C) Cationic polymerizable cross-linking agent]
The photosensitive resin composition of the present invention may further contain a cationic polymerizable cross-linking agent as component (C). The cationic polymerizable cross-linking agent is capable of undergoing a cationic polymerization reaction with the epoxy group of the component (A), and is a component for facilitating the formation of a pattern and further increasing the strength of the resin film after photocuring. It is to raise.

As the cross-linking agent, a compound having a molecular weight of 100 to 15,000 is preferable, and a compound having a molecular weight of 200 to 1,000 is more preferable. If the molecular weight is 100 or more, sufficient photocurability can be obtained. The compound may be a resin (polymer), in which case the molecular weight is the weight average molecular weight (Mw).

As the cationic polymerizable cross-linking agent, a compound having a functional group selected from an epoxy group, an oxetane group and a vinyl ether group is preferable. You may use these compounds individually by 1 type or in combination of 2 or more types.

The content of component (C) is 0 to 100 parts by mass with respect to 100 parts by mass of component (A). is more preferred, and 1 to 50 parts by mass is even more preferred. If the content of component (C) is 0.5 parts by mass or more, sufficient curability is obtained upon irradiation with light, and if it is 100 parts by mass or less, the proportion of component (A) in the photosensitive resin composition is Since it does not decrease, the effect of the present invention can be exhibited sufficiently in the cured product. (C) component can be used individually by 1 type or in combination of 2 or more types.

[(D) Solvent]
The photosensitive resin composition of the present invention may contain a solvent as the component (D) in order to improve its coatability. The solvent (D) is not particularly limited as long as it can dissolve components (A) to (C) described above, component (E) described later, and various other additives.

(D) The solvent is preferably an organic solvent, and specific examples thereof include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; 3-methoxybutanol, 3-methyl-3-methoxybutanol; , 1-methoxy-2-propanol, 1-ethoxy-2-propanol and other alcohols; propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc. Ethers of; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-propionate Examples include esters such as butyl, propylene glycol-mono-tert-butyl ether acetate, γ-butyrolactone, and the like. These may be used individually by 1 type, and may be used in mixture of 2 or more types.

As the solvent (D), ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, and a mixed solvent thereof, which are particularly excellent in dissolving the photoacid generator, are preferred.

When component (D) is included, the content thereof is preferably 50 to 2,000 parts by mass, preferably 50 to 1 ,000 parts by mass, more preferably 50 to 100 parts by mass.

[(E) Antioxidant]
The photosensitive resin composition of the present invention may contain an antioxidant as an additive. Heat resistance can be improved by including an antioxidant. Examples of the antioxidant include hindered phenol compounds and hindered amine compounds.

Although the hindered phenol compound is not particularly limited, the following compounds are preferable. For example, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (trade name: IRGANOX 1330), 2,6-di-tert- Butyl-4-methylphenol (trade name: Sumilizer BHT), 2,5-di-tert-butyl-hydroquinone (trade name: Nocrac NS-7), 2,6-di-tert-butyl-4-ethylphenol ( (trade name: Nocrac M-17), 2,5-di-tert-pentylhydroquinone (trade name: Nocrac DAH), 2,2′-methylenebis(4-methyl-6-tert-butylphenol) (trade name: Nocrac NS) -6), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester (trade name: IRGANOX 1222), 4,4'-thiobis(3-methyl-6-tert-butylphenol) (trade name: Nocrac 300), 2,2′-methylenebis(4-ethyl-6-tert-butylphenol) (trade name: Nocrac NS-5), 4,4′-butylidenebis(3-methyl-6-tert- butylphenol) (trade name: Adekastab AO-40), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM), 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate (trade name: Sumilizer GS), 2,2′-methylenebis[ 4-methyl-6-(α-methyl-cyclohexyl)phenol], 4,4′-methylenebis(2,6-di-tert-butylphenol) (trade name: Synox 226M), 4,6-bis(octylthio Methyl)-o-cresol (trade name: IRGANOX 1520L), 2,2'-ethylenebis(4,6-di-tert-butylphenol), octadecyl-3-(3,5-di-tert-butyl-4- Hydroxyphenyl)propionate (trade name: IRGANOX 1076), 1,1,3-tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (trade name: Adekastab AO-30), tetrakis[methylene -(3,5-di-tert-butyl-4-hydroxy hydrocinnamate)]methane (trade name: Adekastab AO-60), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 245), 2 ,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine (trade name: IRGANOX 565), N,N'-hexa methylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide) (trade name: IRGANOX 1098), 1,6-hexanediol-bis[3-(3,5-di-tert- Butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 259), 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1035), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]1,1-dimethylethyl]2,4,8,10-tetra Oxaspiro[5.5]undecane (trade name: Sumilizer GA-80), tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: IRGANOX 3114), bis(3, Ethyl 5-di-tert-butyl-4-hydroxybenzylphosphonate) calcium/polyethylene wax mixture (50:50) (trade name: IRGANOX 1425WL), isooctyl-3-(3,5-di-tert-butyl-4 -hydroxyphenyl)propionate (trade name: IRGANOX 1135), 4,4'-thiobis(6-tert-butyl-3-methylphenol) (trade name: Sumilizer WX-R), 6-[3-(3-tert -Butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphepin (trade name: Sumilizer GP) and the like.

Although the hindered amine compound is not particularly limited, the following compounds are preferable. For example, p,p'-dioctyldiphenylamine (trade name: IRGANOX 5057), phenyl-α-naphthylamine (trade name: Nocrac PA), poly(2,2,4-trimethyl-1,2-dihydroquinoline) (trade name) : Nocrac 224, 224-S), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (trade name: Nocrac AW), N,N'-diphenyl-p-phenylenediamine (trade name: Nocrac DP), N,N'-di-β-naphthyl-p-phenylenediamine (trade name: Nocrac White), N-phenyl-N'-isopropyl-p-phenylenediamine (trade name: Nocrac 810NA), N, N'-diallyl-p-phenylenediamine (trade name: Nonflex TP), 4,4'-(α,α-dimethylbenzyl)diphenylamine (trade name: Nocrac CD), p,p-toluenesulfonylaminodiphenylamine (trade name : Nocrac TD), N-phenyl-N'-(3-methachloryloxy-2-hydroxypropyl)-p-phenylenediamine (trade name: Nocrac G1), N-(1-methylheptyl)-N'-phenyl -p-phenylenediamine (trade name: Ozonon 35), N,N'-di-sec-butyl-p-phenylenediamine (trade name: Sumilizer BPA), N-phenyl-N'-1,3-dimethylbutyl- p-phenylenediamine (trade name: Antigene 6C), alkylated diphenylamine (trade name: Sumilizer 9A), dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethyl succinate Piperidine polycondensate (trade name: Tinuvin 622LD), poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2, 2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]] (trade name: CHIMASSORB 944), N,N'- Bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5 -triazine condensate (trade name: CHIMASSORB 119FL), bis(1-octyloxy- 2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name: TINUVIN 123), bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name: TINUVIN 770), Bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate (trade name: TINUVIN 144 ), bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (trade name: TINUVIN 765), tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2 ,3,4-butane tetracarboxylate (trade name: LA-57), tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate (trade name: LA-57) : LA-52), a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol (trade name: LA-62 ), a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol (trade name: LA-67), 1,2 ,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8, Mixed ester with 10-tetraoxaspiro[5.5]undecane (trade name: LA-63P), 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4 -Piperidinol and mixed ester with 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: LA-68LD ), (2,2,6,6-tetramethylene-4-piperidyl)-2-propylene carboxylate (trade name: Adekastab LA-82), (1,2,2,6,6-pentamethyl-4-piperidyl) )-2-propylene carboxylate (trade name: Adekastab LA-87).

The content of component (E) is not particularly limited as long as it does not impair the effects of the present invention, but when it is included, it is preferably 0.01 to 1% by mass in the photosensitive resin composition of the present invention. The (E) component antioxidant may be used alone or in combination of two or more.

[Other additives]
The photosensitive resin composition of the present invention may contain other additives in addition to the components described above. Additives include, for example, surfactants commonly used to improve coatability.

As the surfactant, a nonionic one is preferable, and examples thereof include fluorine-based surfactants such as perfluoroalkylpolyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, and fluorine-containing organosiloxane. system compounds and the like. Commercially available products can be used, for example, Fluorad (registered trademark) FC-430 (manufactured by 3M), Surflon (registered trademark) S-141 and S-145 (manufactured by AGC Seimi Chemical Co. ), Unidyne (registered trademark) DS-401, DS-4031 and DS-451 (manufactured by Daikin Industries, Ltd.), Megafac (registered trademark) F-8151 (manufactured by DIC Corporation), X-70-093 ( manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Among these, Fluorad FC-430 and X-70-093 are preferred. The content of the surfactant is not particularly limited as long as it does not impair the effects of the present invention, but when it is included, it is preferably 0.01 to 1% by mass in the photosensitive resin composition of the present invention.

A silane coupling agent can also be used as an additive. By including a silane coupling agent, the adhesion of the photosensitive resin composition to the adherend can be further enhanced. Silane coupling agents include epoxysilane coupling agents and aromatic-containing aminosilane coupling agents. These can be used individually by 1 type or in combination of 2 or more types. The content of the silane coupling agent is not particularly limited as long as it does not impair the effects of the present invention.

The method for preparing the photosensitive resin composition of the present invention is not particularly limited, but examples thereof include a method of stirring and mixing the respective components, and then, if necessary, filtering with a filter or the like to remove solids.

[Pattern formation method]
The pattern forming method of the present invention uses the photosensitive resin composition,
(i) forming a photosensitive resin film on a substrate using the photosensitive resin composition described above;
(ii) exposing the photosensitive resin film; and (iii) developing the exposed photosensitive resin film with a developer. A fine pattern can be obtained by this method.

Step (i) is a step of forming a photosensitive resin film on a substrate using the photosensitive resin composition. Examples of the substrate include silicon wafers, glass wafers, quartz wafers, plastic circuit boards, and ceramic circuit boards.

A photosensitive resin film can be formed by a known method. For example, it can be formed by coating the photosensitive resin composition on a substrate by a dipping method, a spin coating method, a roll coating method, or the like. The coating amount can be appropriately selected according to the purpose, but the amount that provides a film thickness of 0.1 to 100 μm is preferable.

Here, in order to perform the photo-curing reaction efficiently, the solvent and the like may be evaporated in advance by preheating as necessary. Preheating can be performed, for example, at 40 to 160° C. for about 1 minute to 1 hour.

Next, as step (ii), the photosensitive resin film is exposed. At this time, exposure is preferably performed with light having a wavelength of 240 to 500 nm. Examples of the light having a wavelength of 240 to 500 nm include light having various wavelengths generated by a radiation generator, such as ultraviolet rays such as g-line and i-line, far ultraviolet rays (248 nm), and the like. The exposure amount is preferably 10 to 5,000 mJ/cm ² .

Exposure may be performed through a photomask. For example, the photomask may be hollowed out in a desired pattern. The material of the photomask is preferably one that blocks the light with a wavelength of 240 to 500 nm. For example, chromium is preferably used, but the material is not limited to this.

Furthermore, in order to increase development sensitivity, heat treatment (PEB) may be performed after exposure. PEB can be, for example, 40-160° C. for 5-30 minutes.

Step (iii) is a step of developing the photosensitive resin film with a developer after exposure or PEB. The developer is preferably an organic solvent-based developer used as a solvent, such as isopropyl alcohol, propylene glycol monomethyl ether, or propylene glycol monomethyl ether acetate. By developing with the organic solvent-based developer, a negative pattern in which the non-exposed areas are dissolved and removed can be obtained. The development can be carried out by a usual method, for example, by immersing the patterned substrate in the developer. Thereafter, washing, rinsing, drying, etc. are performed as necessary to obtain a film having a desired pattern.

The method of forming a pattern is as described above. However, if there is no need to form a pattern, for example, if it is desired to form a simple uniform film, the photomask may be used in the step (ii) of the pattern forming method. Instead, the film can be formed by exposing to light of an appropriate wavelength.

Furthermore, if necessary, (iv) the patterned film is further heated at 120 to 300 ° C. using an oven or hot plate for about 10 minutes to 10 hours to increase the crosslink density and remove the remaining volatilization. A treatment for removing components (post-curing) may be performed.

[Optical semiconductor device]
An optical semiconductor device can be produced by forming a fine pattern using the photosensitive resin composition by the method described above. In addition, the film obtained from the photosensitive resin composition is excellent in transparency, light resistance and heat resistance, and the optical semiconductor device provided with the film is a light emitting device such as a light emitting diode, a photodiode, an optical sensor, a CMOS image sensor. and optical devices such as optical transmission devices such as optical waveguides. The coating preferably has a transmittance of 92% or more, more preferably 96% or more, and particularly preferably 98% or more, for light having a wavelength of 405 nm.

EXAMPLES The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, Mw was measured using TSKGEL Super HZM-H (manufactured by Tosoh Corporation) as a GPC column under the analysis conditions of a flow rate of 0.6 mL/min, an elution solvent of THF, and a column temperature of 40°C. It was measured by GPC using polystyrene as a standard.

Compounds (S-1), (S-2a), (S-2b), (S-3a), (S-3b), (S-4), (S-5) and ( S-6) is as follows.

[1] Synthesis of polymer and its evaluation (1) Synthesis of polymer [Example 1-1] Synthesis of polymer 1 Compound (S-4) was placed in a 10 L flask equipped with a stirrer, thermometer, nitrogen replacement device and reflux condenser. After adding 132.5 g (0.50 mol) and 269.5 g (0.50 mol) of compound (S-3a), 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 116.4 g (0.60 mol) of compound (S-1) and 1,208.0 g of compound (S-2a) were added. (0.40 mol) was added dropwise over 1 hour (total hydrosilyl groups/total alkenyl groups=1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, and toluene was distilled off from the reaction solution under reduced pressure to obtain polymer 1 (siloxane unit content: 70.0% by mass). The Mw of Polymer 1 was 43,000. Polymer 1 was confirmed by ¹ H-NMR (manufactured by Bruker) to be a polymer containing repeating units A1 to A4.

[Example 1-2] Synthesis of Polymer 2 Into a 10 L flask equipped with a stirrer, thermometer, nitrogen purge device and reflux condenser, 79.5 g (0.30 mol) of compound (S-4) and compound (S-4) were added. 3a) 377.3 g (0.70 mol) was added, followed by 2,000 g of toluene and heated to 70°C. Then, 1.0 g of chloroplatinic acid toluene solution (platinum concentration: 0.5% by mass) was added, and 174.6 g (0.90 mol) of compound (S-1) and 158.5 g (0.90 mol) of compound (S-2b) .10 mol) was added dropwise over 1 hour (total hydrosilyl groups/total alkenyl groups=1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, then toluene was distilled off from the reaction solution under reduced pressure to obtain polymer 2 (siloxane unit content: 20.1% by mass). The Mw of Polymer 2 was 83,000. Polymer 2 was confirmed by ¹ H-NMR (manufactured by Bruker) to be a polymer containing repeating units A1 to A4.

[Example 1-3] Synthesis of polymer 3 Into a 10 L flask equipped with a stirrer, thermometer, nitrogen purge device and reflux condenser, 26.5 g (0.10 mol) of compound (S-4) and compound (S-4) were added. 3a) 485.1 g (0.90 mol) was added, followed by 2,000 g of toluene and heated to 70°C. Then, 1.0 g of chloroplatinic acid toluene solution (platinum concentration: 0.5% by mass) was added, and 135.8 g (0.70 mol) of compound (S-1) and 475.5 g (0.70 mol) of compound (S-2b) .30 mol) was added dropwise over 1 hour (total hydrosilyl groups/total alkenyl groups=1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, and toluene was distilled off from the reaction solution under reduced pressure to obtain polymer 3 (siloxane unit content: 42.3% by mass). The Mw of polymer 3 was 8,000. Polymer 3 was confirmed by ¹ H-NMR (manufactured by Bruker) to be a polymer containing repeating units A1 to A4.

[Example 1-4] Synthesis of Polymer 4 Into a 10 L flask equipped with a stirrer, thermometer, nitrogen purge device and reflux condenser, 238.5 g (0.90 mol) of compound (S-4) and compound (S-4) were added. 3a) 53.9 g (0.10 mol) was added, followed by 2,000 g of toluene and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 155.2 g (0.80 mol) of compound (S-1) and 604.0 g (0.80 mol) of compound (S-2a) 20 mol) was added dropwise over 1 hour (total hydrosilyl groups/total alkenyl groups=1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, and toluene was distilled off from the reaction solution under reduced pressure to obtain polymer 4 (siloxane unit content: 57.4% by mass). The Mw of polymer 4 was 143,000. Polymer 4 was confirmed by ¹ H-NMR (manufactured by Bruker) to be a polymer containing repeating units A1 to A4.

[Example 1-5] Synthesis of polymer 5 Into a 10 L flask equipped with a stirrer, thermometer, nitrogen purge device and reflux condenser, 185.5 g (0.70 mol) of compound (S-4) and compound (S-4) were added. 3b) 254.5 g (0.30 mol) was added, followed by 2,000 g of toluene and heated to 70°C. Then, 1.0 g of chloroplatinic acid toluene solution (platinum concentration: 0.5% by mass) was added, and 77.6 g (0.40 mol) of compound (S-1) and 951.0 g (0.40 mol) of compound (S-2b) .60 mol) was added dropwise over 1 hour (total hydrosilyl groups/total alkenyl groups=1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, then toluene was distilled off from the reaction solution under reduced pressure to obtain polymer 5 (siloxane unit content: 65.2% by mass). The Mw of polymer 5 was 23,000. Polymer 5 was confirmed by ¹ H-NMR (manufactured by Bruker) to be a polymer containing repeating units A1 to A4.

[Example 1-6] Synthesis of polymer 6 Into a 10 L flask equipped with a stirrer, thermometer, nitrogen purge device and reflux condenser, 132.5 g (0.50 mol) of compound (S-4) and compound (S-4) were added. 3b) 409.0 g (0.50 mol) was added, followed by 2,000 g of toluene and heated to 70°C. Then, 1.0 g of chloroplatinic acid toluene solution (platinum concentration: 0.5% by mass) was added, and 174.6 g (0.90 mol) of compound (S-1) and 302.0 g (0.90 mol) of compound (S-2a) .10 mol) was added dropwise over 1 hour (total hydrosilyl groups/total alkenyl groups=1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, and toluene was distilled off from the reaction solution under reduced pressure to obtain polymer 6 (siloxane unit content: 29.7% by mass). The Mw of polymer 6 was 103,000. Polymer 6 was confirmed by ¹ H-NMR (manufactured by Bruker) to be a polymer containing repeating units A1 to A4.

[Comparative Example 1-1] Synthesis of Comparative Polymer 1 212.0 g (0.80 mol) of compound (S-4) and compound (S -6) After adding 86.0 g (0.20 mol), 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of chloroplatinic acid toluene solution (platinum concentration: 0.5% by mass) was added, and 184.3 g (0.95 mol) of compound (S-1) and 79.3 g (0.95 mol) of compound (S-2b) .05 mol) was added dropwise over 1 hour (total hydrosilyl groups/total alkenyl groups=1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, and toluene was distilled off from the reaction solution under reduced pressure to obtain Comparative Polymer 1 (siloxane unit content: 14.1% by mass). The Mw of Comparative Polymer 1 was 8,000.

[Comparative Example 1-2] Synthesis of Comparative Polymer 2 212.0 g (0.80 mol) of compound (S-4) and compound (S -5) After adding 78.4 g (0.20 mol), 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 38.8 g (0.20 mol) of compound (S-1) and 1,268.0 g of compound (S-2b) were added. (0.80 mol) was added dropwise over 1 hour (total hydrosilyl groups/total alkenyl groups=1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, and toluene was distilled off from the reaction solution under reduced pressure to obtain Comparative Polymer 2 (siloxane unit content: 79.4% by mass). The Mw of Comparative Polymer 2 was 85,000.

[Comparative Example 1-3] Synthesis of Comparative Polymer 3 431.2 g (0.80 mol) of compound (S-3a) and compound (S -6) After adding 86.0 g (0.20 mol), 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of chloroplatinic acid toluene solution (platinum concentration: 0.5% by mass) was added, and 174.6 g (0.90 mol) of compound (S-1) and 158.5 g (0.90 mol) of compound (S-2b) .10 mol) was added dropwise over 1 hour (total hydrosilyl groups/total alkenyl groups=1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, and toluene was distilled off from the reaction solution under reduced pressure to obtain Comparative Polymer 3 (siloxane unit content: 18.6% by mass). The Mw of Comparative Polymer 3 was 28,000.

[Comparative Example 1-4] Synthesis of Comparative Polymer 4 654.4 g (0.80 mol) of compound (S-3b) and compound (S -5) After adding 78.4 g (0.20 mol), 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of chloroplatinic acid toluene solution (platinum concentration: 0.5% by mass) was added, and 174.6 g (0.90 mol) of compound (S-1) and 302.0 g (0.90 mol) of compound (S-2a) .10 mol) was added dropwise over 1 hour (total hydrosilyl groups/total alkenyl groups=1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, and toluene was distilled off from the reaction solution under reduced pressure to obtain Comparative Polymer 4 (siloxane unit content: 25.0% by mass). The Mw of Comparative Polymer 4 was 59,000.

[Comparative Example 1-5] Synthesis of Comparative Polymer 5 215.0 g (0.50 mol) of compound (S-6) and compound (S -5) After adding 196.0 g (0.50 mol), 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of chloroplatinic acid toluene solution (platinum concentration: 0.5% by mass) was added, and 135.8 g (0.70 mol) of compound (S-1) and 906.0 g (0.70 mol) of compound (S-2a) .30 mol) was added dropwise over 1 hour (total hydrosilyl groups/total alkenyl groups=1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, then toluene was distilled off from the reaction solution under reduced pressure to obtain Comparative Polymer 5 (siloxane unit content: 62.4% by mass). The Mw of Comparative Polymer 5 was 93,000.

[Comparative Example 1-6] Synthesis of Comparative Polymer 6 After adding 430.0 g (1.00 mol) of compound (S-6) to a 10 L flask equipped with a stirrer, a thermometer, a nitrogen purge device and a reflux condenser, , 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 155.2 g (0.80 mol) of compound (S-1) and 604.0 g (0.80 mol) of compound (S-2a) 20 mol) was added dropwise over 1 hour (total hydrosilyl groups/total alkenyl groups=1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, then toluene was distilled off from the reaction solution under reduced pressure to obtain Comparative Polymer 6 (siloxane unit content: 50.8% by mass). The Mw of Comparative Polymer 6 was 67,000.

[Comparative Example 1-7] Synthesis of Comparative Polymer 7 After adding 392.0 g (1.00 mol) of compound (S-5) to a 10 L flask equipped with a stirrer, a thermometer, a nitrogen purge device and a reflux condenser, , 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 155.2 g (0.80 mol) of compound (S-1) and 604.0 g (0.80 mol) of compound (S-2a) 20 mol) was added dropwise over 1 hour (total hydrosilyl groups/total alkenyl groups=1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, and toluene was distilled off from the reaction solution under reduced pressure to obtain Comparative Polymer 7 (siloxane unit content: 52.5% by mass). The Mw of Comparative Polymer 7 was 100,000.

[Comparative Example 1-8] Synthesis of Comparative Polymer 8 After adding 265.0 g (1.00 mol) of compound (S-4) to a 10 L flask equipped with a stirrer, a thermometer, a nitrogen purge device and a reflux condenser, , 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 155.2 g (0.80 mol) of compound (S-1) and 604.0 g (0.80 mol) of compound (S-2a) 20 mol) was added dropwise over 1 hour (total hydrosilyl groups/total alkenyl groups=1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, and toluene was distilled off from the reaction solution under reduced pressure to obtain Comparative Polymer 8 (siloxane unit content: 59.0% by mass). The Mw of Comparative Polymer 8 was 70,000.

(2) Light transmittance test [Examples 2-1 to 2-6]
Each of Polymers 1 to 6 was dissolved in cyclopentanone to a concentration of 50% by mass to prepare a resin solution. Each resin solution was applied onto a glass wafer, heated at 60° C. for 30 minutes, and further heated at 190° C. for 2 hours in a nitrogen atmosphere to form a resin film (thickness: 10 μm). The obtained film was measured for light transmittance at a wavelength of 405 nm using a spectrophotometer U-3900H (manufactured by Hitachi High-Tech Science Co., Ltd.). Table 1 shows the results.

A sample consisting of a film on a glass wafer obtained by the above method was irradiated with a 1 W laser at a wavelength of 405 nm in an oven at 50 ° C. for 100 hours. Transmittance was measured. Table 2 shows the results.

From the above results, according to the present invention, novel polymers such as Polymers 1 to 6 having a polysiloxane skeleton, a silphenylene skeleton, an isocyanuric acid skeleton and a polyether skeleton in the main chain could be synthesized. A coating obtained from the siloxane polymer of the present invention can be used as a coating with high transparency and high light resistance.

[2] Preparation of photosensitive resin composition and its evaluation [Examples 3-1 to 3-10, Comparative Examples 2-1 to 2-19]
(1) Preparation of photosensitive resin composition Polymers 1 to 6 as component (A), comparative polymers 1 to 8, and photoacid generator B as component (B) so that the compositions shown in Tables 3 to 5 below are obtained. -1, B-2, crosslinking agent C-1, C-2, C-3 as component (C), cyclopentanone (CP) as solvent for component (D), E as antioxidant for component (E) -1 and E-2 were mixed, then stirred and dissolved, followed by microfiltration through a Teflon (registered trademark) 0.2 μm filter to prepare a photosensitive resin composition.

In Tables 3 to 5, photoacid generators B-1 and B-2, cross-linking agents C-1, C-2 and C-3, and antioxidants E-1 and E-2 are as follows. .
- Photoacid generator B-1:

・ Photoacid generator B-2: CPI210S manufactured by San-Apro Co., Ltd.

- Crosslinking agents C-1, C-2, C-3:

· Antioxidant E-1: CHIMASSORB 119FL (manufactured by BASF)

· Antioxidant E-2: IRGANOX 3114 (manufactured by BASF)

(2) Pattern Formation Evaluation Each photosensitive resin composition was coated to a film thickness of 10 μm using a spin coater on an 8-inch silicon wafer primed with hexamethyldisilazane. To remove the solvent from the composition, the wafer was placed on a hotplate, heated at 110° C. for 3 minutes, and dried. In order to form a line-and-space pattern and a contact hole pattern on the obtained photosensitive resin film, the film was exposed through a mask under the exposure condition of 365 nm using a contact aligner type exposure apparatus. After the light irradiation, the wafer was subjected to PEB at 120° C. for 3 minutes with a hot plate and then cooled, and the wafer was subjected to spray development with propylene glycol monomethyl ether acetate (PGMEA) for 300 seconds to form a pattern.

The photosensitive resin film on the wafer on which the pattern was formed by the above method was post-cured in an oven at 190° C. for 2 hours while purging with nitrogen. Then, using a scanning electron microscope (SEM), the cross sections of the formed contact hole patterns of 50 μm, 30 μm, 20 μm, 10 μm, and 5 μm were observed, and the smallest hole pattern in which the holes penetrated to the bottom of the film was found with the limit resolution. and Further, the verticality of the 50 μm contact hole pattern was evaluated from the obtained cross-sectional photograph, and the vertical pattern was evaluated as ⊚, the slightly reverse tapered shape as ◯, the reverse tapered shape as Δ, and the poor opening as x. The results are shown in Tables 6-8.

(3) Light transmittance test 1
An 8-inch glass wafer was coated with each photosensitive resin composition to a film thickness of 20 μm using a spin coater. To remove the solvent from the composition, the glass wafer was placed on a hot plate, heated at 110° C. for 3 minutes, and dried. The entire surface of the composition applied to the glass wafer is irradiated with light from a high-pressure mercury lamp (wavelength: 360 nm) using a mask aligner MA8 manufactured by SUSS MICROTECH without a mask, followed by PEB and PGMEA. immersed in The film remaining after this operation was further heated in an oven at 190° C. for 2 hours to obtain a film. For this film, the transmittance of light with a wavelength of 405 nm was measured using a spectrophotometer U-3900H (manufactured by Hitachi High-Tech Science Co., Ltd.). The results are shown in Tables 9-11.

(4) Light transmittance test 2
(3) A sample made of a film on a glass wafer obtained by the same method as in light transmittance test 1 was continuously irradiated with a 405 nm, 1 W laser in an oven at 150 ° C., and the initial time was set to 100%. The change in light transmittance after 2,000 hours at a wavelength of 405 nm was investigated. The results are shown in Tables 12-14.

(5) Evaluation of reliability (adhesion, crack resistance) (3) A wafer with a photosensitive resin film obtained by the same method as in light transmission test 1 was cut with a dicing saw (DAD685, manufactured by DISCO) equipped with a dicing blade. , spindle rotation speed of 40,000 rpm, cutting speed of 20 mm/sec) to obtain a 10 mm x 10 mm square test piece. The obtained test pieces (10 pieces each) were subjected to a heat cycle test (repeated 2,000 cycles of holding at -25 ° C. for 10 minutes and holding at 125 ° C. for 10 minutes), and the resin film after the heat cycle test. The state of separation from the wafer and the presence or absence of cracks were checked. Those with no peeling or cracking were evaluated as good, those with at least one peeling were evaluated as peeled, and those with at least one crack were evaluated as cracked. The results are shown in Tables 15-17.

From the above results, the photosensitive resin composition of the present invention is capable of fine pattern formation and exhibits sufficient characteristics as a photosensitive material, and the film has high light transmittance and good light resistance and reliability. properties (adhesion, crack resistance) and is useful as a material for optical semiconductor devices.

Claims (14)

A siloxane polymer containing a polysiloxane skeleton, a silphenylene skeleton, an isocyanuric acid skeleton and a polyether skeleton in the main chain and an epoxy group in the side chain, wherein the repeating unit represented by the following formulas (A1) to (A4) A siloxane polymer comprising:

[In the formula, R ¹ to R ⁴ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. Each m is independently an integer from 1 to 600. When m is an integer of 2 or more, each R ³ may be the same or different, and each R ⁴ may be the same or different. a1 , a2 ^, a3 and a4 are ⁰ < a1 <1 ^{, 0} <a2< ¹ , 0< ^a3 < ¹ , ⁰ <a4 < ¹ and a1 + ^a2 + ^a3 + ^a4 = 1 is a number that satisfies. X ¹ is a divalent group represented by the following formula (X1). X ² is a divalent group represented by the following formula (X2).

(wherein R ¹¹ and R ¹² are each independently a hydrogen atom or a methyl group; n ¹ and n ² are each independently an integer of 0 to 7; R ¹³ has 1 to 8 divalent hydrocarbon group, which may contain an ester bond or an ether bond between its carbon atoms.)

(wherein R ²¹ and R ²² are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms; R ²³ and R ²⁴ are each independently a hydrogen atom or a methyl group; p ¹ and p ² are each independently an integer of 1 to 6. q is an integer of 1 to 100.)] 2. The siloxane polymer according to claim 1, wherein the transmittance of light having a wavelength of 405 nm in a 10 μm-thick film made of said polymer is 97% or more. The siloxane polymer according to claim 1 or 2, wherein q is an integer of 1-50. The siloxane polymer of claim 3, wherein q is an integer from 5-20. The siloxane polymer according to any one of claims 1 to 4, wherein m is an integer of 10-100. A siloxane polymer according to any one of claims 1 to 5, wherein R ¹¹ , R ¹² , R ²¹ and R ²² are hydrogen atoms. The siloxane polymer according to any one of claims 1 to 6, which has a weight average molecular weight of 3,000 to 500,000. (A) A photosensitive resin composition comprising the siloxane polymer according to any one of claims 1 to 7 and (B) a photoacid generator. 9. The photosensitive resin composition according to claim 8, wherein the content of component (B) is 0.05 to 20 parts by mass per 100 parts by mass of component (A). 10. The photosensitive resin composition according to claim 8, further comprising (C) a cationic polymerizable cross-linking agent. The photosensitive resin composition according to any one of claims 8 to 10, further comprising (D) a solvent. The photosensitive resin composition according to any one of claims 8 to 11, further comprising (E) an antioxidant. (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition according to any one of claims 8 to 12;
(ii) a step of exposing the photosensitive resin film; and (iii) a step of developing the exposed photosensitive resin film using a developer. A method for manufacturing an optical semiconductor element having a photosensitive resin film, comprising the pattern forming method according to claim 13 .